Monoazo-dyestuffs insoluble in water



Patented Nov. 5, 1940 UNITED STATES PATENT. critics.

MONOAZO-DYESTUFFSINS-OLUBLEIN 7 I I WATER; v r

Ernst Fischer, OiTenbach-on-the-Main, Germany, 1

assignor to General Aniline & Filin' Corporation, a, corporation ofDelaware s No Drawing. Application June""2,i 1939, Serial No.2'7'7,017.In Germany June-4,1938

5 Claims.

The present inventionrelates to monoaZo-dyestufi's insoluble in water;more particularly it relates to dyestufis of the following generalformula:

Y-O NZ 1 N wherein X represents the group 'CO- or SO2-, R1 and R2represent alkyl-, -aralkyl-,

arylor-hydroaromatic radicals which-may beconnected to form aheterocylic ring system; Y

stands for methyl, a' carboxlic acid ester group" or phenyl, and Z for aradicalcof the benzene series, and wherein-the benzeneradical-a may befurther substituted byalkyl-,' alkoXy-, aryloxygroups or halogen atoms.a

I have found that valuable pigmentdyestuffs may-be obtained by couplingwith a 1-aryl-'3= methyI-S-pyrazolone, a '1-aryl 3-aryl-5-pyrazo lone, a1-aryl-5-pyrazolone3-carboxylic acid estersor a substitutionproduct-thereof the diazocompound from an amine of the general for mula:

Y-XN

where X represents the group CO- or --SOz-, R1 and R2 represent alkyl-,'aralkyl-, aryl' or hydroaromatic radicals which 'may be connected in aheterocyclic ring system,and-wh'erein' the benzene radicala may befurther'substituted by alkyl-, alkoxy-, aryloxy-groups orhalogenatoms,

only'such dyestufi components :being used as do* not contain any grouplendingsolubility in water, such as the sulfonic or carboxylic acidgroup.

The new dyestuffs yield vivid yellow and orange tints of goodproperties'offastness,;especially of goodfastnessto--light; They; areinsoluble in water, butvery easilysoluble'in" many bility in organicsolvents, p artly'by their considerably better fastness properties; suchas higher fastness'to light; the "dyeings produced on rubber by means ofthe new-dyestuffs bleed during the vulcanisation'process to aconsiderably small er extent. 1 g V p The following examples serve toillustrate the invention, but they are not intended to limit it thereto;the parts are by weight:

1. 9.6 parts of; lamino=benz'ene-'2-(carbonyl-d1 ethylamine) arediazotized in the usual manner. In order to bind the excess of mineralacid, so dium acetate is added to the diazo-solutionand the whole isthen stirred into an aqueous suspen- 1 sion of 8.7 parts of1-phenyl-3-rnethyl 5-pyrazolone prepared by dissolving this-compound indilute caustic soda solution andreprecipitating it by means of aceticacid. When the coupling is 'complete,'the-dyestufi formed is filteredwith suction, washed Welland dried, It is a yellow 1 powder which easilydissolves in acetone, butyl acetate and Otherbrganicsolvents to ayellowsolution and'colors cellulose ester lacquers vivid and fast tints.The dyestufi corresponds with the 1 [following formula.

'2." 1012f parts of" 1-aminobenz ene-2 (carbonylsolution is made neutralto Congo paper by means of sodium acetate, and then stirred into asuspension of 9.4 parts of 1-(4'-methylpheny1) 3- methyl-5-pyrazoloneprepared by dissolving this compound in dilute caustic soda solution andreprecipitating it by means of acetic acid. The

dyestufi formed is filtered with suction, washed well and dried. Itdissolves easily in ethyl alcohol, xylene and other organic solvents andcolors nitrocellulose lacquers and acetylcellulose lacquers as well asvarnishes vivid yellow tints of good fastness to light.

3. If there are used, in Example 1, instead of 8.7 parts of1-phenyl-3-methyl-5-pyrazo1one, 11.6 parts of1-phenyl-5-pyrazolone-3-carboxylic acid ethyl ester, a yellow dyestufihaving similar properties is obtained; it colors the various organicsolvents and the lacquers prepared by means of these solvents as well ascandles and fats yellow tints.

4. A yellow dyestuff is prepared, in the manner described in Examples 1and 2,; from the diazocompound of 11.4 parts of l-amonobenzene-Z-(sulfonyl-diethyl-amine) and 12.2 parts of 1- (2'.5' -dichlorophenyl)-3-methyl 5 pyrazolone. It dissolves easily in organic solvents andcolors plastic masses and lacquers prepared by means of these solventsas well as candles and fats greenish yellow tints of good fastness tolight.

5. A pigment dyestufi is prepared, in the manner described in Example1,-from the diazo-compound of 9.6 parts ofl-aminobenzene-Z-(carbonyl-diethylamine) and 12.8 'parts of1.3-diphenyl-5-pyrazo1one. It dissolves easily in butyl alcohol, butylacetate and acetone and colors cellulose ester lacquers, varnishes,candles and fats yellow tints which are more reddish than thoseobtainable with the dyestufi of Example 1.

The following table illustrates a number of other mono-azo-dyestufisobtainable by the pres- "ent invention which are likewise easily solublein solvents usually applied for these purposes an have good propertiesof iastness.

lies, it is to be understood that the aromatic nuclei of the generalformulae appearing in the appended claims do not contain anysubstituents which are known to render organic compounds soluble inwater or alkalies and to tend to depreciate the fastness of thedyestuffs to alkalies. Substituents of this kind are, for instance, thesulfonic acid and the carboxylic acid group.

I claim:

1. The water-insoluble monoazo-dyestufl's of the following generalformula:

wherein X represents one of the groups CO and SO2--, R1 and R2 stand formembers of the group consisting of alkyl, benzyl, radicals of thebenzene and naphthalene series and hydroaromatic radicals, which may beconnected to form a heterocyclic ring system; a1 stands for a member ofthe group consisting of hydrogen, alkyl, alkoxy, .phenoxy and halogen,and oz for a member of the group consisting of hydrogen and alkyl; Ystands for a member of the groupconsis-ting of methyl, carboxylic acidester and phenyl, and Z for a radical of the benzene series, beinginsoluble-in water, but very easily soluble Since an object of thepresent invention is toprovide dyestuffs of good fastness propertieswhich dyestuffs are insoluble in water and alka- Diazo-compound irom-Coupled with- Shade 1l-aminobenzene-Z-(carbonyl-N-ethyl-cyclohexylamine)1-(4'-methylphenyl)-3-methyl-5-pyrazolone .Yellow 2l-amm?benzene-2-(sulfony1-N-(n)-butyl-[2-methyl]-phenyla- 1-(2-methylphenyl)-3-methy1-5-pyrazolone Do.

mine 3 do 1-(2.5-dich1oropheny1)-3-methyl5-pyrazo1one Do. 41-ammobenzeue-2-(su1fonyl-d1benzy1amme)1-(2-ch1orophenyl)-3-methyl-5-pyrazolone Do. 51-aminobenzene-2-sulfonyl-N-bepzyl-cyclohexylamine)l-phenyl-Ii-methyl-fi-pyrazolone D0. 6 l-ami nobenzene-2-carbonyl-N-plpendlne) 1-phenyl-fi-pyrazolone-3-carboxylic acid ethylester Do. 7 1-ammo-3-methylbeuzene-6-(carbonyl-dlmethylamlne)l-phenyl-3-methyl-apyrazolone Do. 8l-aminO-B-methyIbenZene-G-(carbonyl-N-benzylphenylamine) dn Do. 9l-amino-E-methylbcnzene-S-(carbonyl-dicyclo-hexylamine) do D 10l-amino-Ii-methylbenzene-d(carbonyl-diphenylamine) Do, 11l-amin)-4-chlor0benzene-6-(carbonyl-N-phenyl-2'-naphthyl- D amine 12l-aminoi-chlorobenzene-6-(carbonyl-N-carbazole) do D 13 l-aminoi-phenoxybenzene-G-(carbonyl-N-methyl-benzylamine).l-(4-methyl-phenyl)-3-methyl-5-pyrazolone Do. 141-aminol-methoxybenzene-6-(sulfonyl-n-dibutylamine) D0. 15l-amino-4-ethoxybenzene-6-(sulfonyl-diethylamine)1-(4'-chloro-phenyl)-3-methyl-5-pyrazolone Do. 16l-amino33-methyl-4-chlorobenzene-6-(sulfonyl-N-methyl-phenyldn Do, lamine 17 1-aminobenzene-2-(carbonyl-dibenzylamine) 1-henyl--pyrazolone-S-carboxylic acid ethyl ester Do. 18i-aminobenzene-2-(carbonyl-N-ethyl-cyc1ohexylamine) l-3'-nitropheny1)-3-methy1-5-pyrazolone Do. 191-amino-s-methoxybenzene-fi-(carbonyl-nfdibutylamine)1-phenyl-3-methyl-5-pyrazolone Do. 20 l-amino-8-methoxybenzene-6-(carbonyl-drethylamine) dn D 21 n v l-phenyl-5- yrezolone-3-carboxylicacid ethyl est Do. 22 d0 l-22-ch1oro -phenyl-B-methyl-S-pyrazolone Do.23 do i 1- 2.5'-dichloro)-phenyl-3-methy1-5-pyrazolone. Do. 24i-amino-Zi-ethoxybenzene-fi-(carbonyl-dlethylamme) do D 25i-zminobenzene-Z-(sulfonyl-dimethylamine)1-(2-methyl-6-ch1oro)-phenyl-3-methyl-6-pyrazolono Do. 26l-agiiilio-s-methylbenzene-fi-(carbonyl-N-phenyl-2'-naphl-phenyl-a-methyl-fi-pyrazoloneDo.

t y amlne. V 1 271-amino-i-chlorobenzene-fi-(carbonyl-N-methyl-benzylamine) I Do, 281-amino-3-methyl-4-chlorobenzene-6-(sulfonyl-n-dibutylamine) do Do. 291-aminobenzene-2-(sulfonyl-dlmethylamine)1-(2-chloro)-phenyl-3-methyI-5-pyrazolone; Do.

pecially of good fastness to light,

2. The water-insoluble monoazo-dyestuffs of the following generalformula:

alkyl XN\ alkyl N OH wherein X represents one of the groups -CO- andSO2, a stands for a member of the group consisting of hydrogen, alkyl,alkoxy, phenoxy and halogen, Y stands for a member of the groupconsisting of methyl, carboxylic acid ester and phenyl, and Z for aradical of the benzene series, being insoluble in water, but very easilysoluble in organic solvents and yielding vivid yellow and orange tintsof good properties of fastness, especially of good fastness to light.

3. The water-insoluble monoazo-dyestufi of the following formula:

being a yellow powder which dissolves easily in organic solvents, suchas acetone, xylene, butyl acetate, butyl alcohol and colors, forinstance, cellulose ester lacquers yellow tints.

4. The water-insoluble monoazo-dyestuff of the following formula:

CzHs

C ON

- CzH5 t E E l CzHsO 0 0-0 N-CsHE being a yellow powder which dissolveseasily in organic solvents, such as acetone, Xylene, butyl acetate,butyl alcohol and colors, for instance, cellulose ester lacquers yellowtints.

ERNST FISCHER.

